JP4128874B2 - New polymer blend - Google Patents

Abstract

A thermoplastic molding composition especially suitable for preparing optical data carriers is disclosed. The composition contains polycarbonate resin, at least one mold release agent and at least one phosphite having a defined structural formula. The optical data carriers include compact discs, video discs, digital versatile discs and further optical data carriers which may be written and erased one or more times.

Description

Detailed Description of the Invention

  The present application relates to novel thermoplastic polymer mixtures containing polycarbonate, mold release agents and specific phosphites, and molded articles, in particular optical data carriers such as compact discs, video discs, digital versatile discs, and writing And the use of the polymer mixture to produce optical data carriers other than those that can be erased one or more times, and molded articles produced therefrom (see above).

  Polycarbonate is generally used as a material for injection molding or injection-press molding optical data carriers with a special combination of properties such as transparency, heat resistance and dimensional stability. Additives such as mold release agents and stabilizers are added to the polycarbonate in order to improve processability generally performed at 300 ° C to 400 ° C.

  An aliphatic fatty acid ester of a polyhydric alcohol, for example, an ester of glycerol and a long chain fatty acid, or an ester of pentaerythritol and a long chain fatty acid is preferably used as a release agent. These esters may be partially esterified, in which case they have a free OH group, which is clearly advantageous for the release action. However, it is necessary to add a stabilizer because the ester reduces the thermal stability of the mixture. Moreover, this stabilizer must be very effective. That is, the stabilizer must be effective at very low concentrations. This is because there is a risk of forming a coating in the mold otherwise. In this case, the mold and die must often be cleaned during processing, which is detrimental and results in low quality sheets. On the other hand, fully esterified release agents have a high degree of stability, but the release action of these esters at low concentrations is much weaker than esters with free OH groups. Therefore, in general, a larger amount of fully esterified release agent must be used, which increases the risk of film formation, but on the other hand, the amount of added stabilizer is somewhat less.

Several mixtures have already been proposed in the literature as follows.
For stabilizing mixtures containing release agents with OH groups, EP-A-205192 describes the use of mixtures of trimethyl phosphate and / or triethyl phosphate and phosphites. Taught. As a result, the stabilizing effect of phosphate esters or phosphites alone is insufficient, and these phosphate esters are ecologically undesirable.

  JP 62-184639 describes an optical data memory produced from polycarbonate stabilized with phosphite. Preference is given to volatile phosphites such as trimethyl phosphite which are ecologically undesirable and critical in film formation.

  JP 2000-80261 describes a polycarbonate mixture containing a release agent, tris (di-tert-butyl-phenyl) phosphite and phosphoric acid. As a result, the stability effect of phosphites is inadequate, so phosphoric acid is used as a further stabilizer, but in high atmospheric humidity and high temperature conditions, the optical data carrier memory layer Corrosion can occur.

  The object of the present invention is therefore to develop a thermoplastic polymer mixture containing polycarbonate, mold release and heat stabilizers, optimized for the production of optical data carriers and other molded articles. That is. In other words, the polymer mixture exhibits a good release action in a small amount, for example. In particular, new disc formats with higher storage capacities and possibly thinner discs such as digital versatile discs (DVDs) require higher thermal stability than CDs. Damage to the material during processing into molded parts and film formation in the mold are more critical.

  With the mixture according to the invention, the object is surprisingly achieved by the large amount of data memory and the improved processability of the material during injection molding or injection molding.

  Accordingly, the present invention relates to a thermoplastic polymer mixture containing at least one polycarbonate, at least one mold release agent, and at least one phosphite represented by a specific chemical structural formula. The phosphite stabilizes the contained release agent even at a low concentration. Therefore, the same release action as described above can be achieved by supplying a smaller amount of the release agent. As a result, film formability is reduced to a surprisingly low level due to the weight loss use of the release agent and its surprisingly high stability.

  The invention relates to the use of the polymer mixture for producing optical data carriers such as compact discs, video discs, digital versatile discs and other optical data carriers which can be written or erased once or more, as well as the polymer mixtures Also relates to optical data carriers manufactured from:

  The polymer blend can obviously be used in other typical polycarbonate applications, including those using higher molecular weight polycarbonates. Said applications may be transparent or opaque, for example food and beverage packages, optical lenses and prisms, lenses for lighting purposes, lenses for automotive headlights, glazing materials for architecture and vehicles, Other various glazing materials such as for greenhouses, so-called double wall sheets or hollow chamber sheets. Examples of applications other than the above include profiles, films, and all types of housing parts (for example, medical devices, juice presses, coffee makers, mixers and other household equipment, computers, monitors, printers, copiers and other office equipment) And for the building industry, seats, pipes, electrical conduits, windows, doors and profiles, interior finishes and external applications), and switches and plugs in the electrical engineering field. The molded articles of the present invention may be used in interior finishes and components of automobiles, ships, aircraft, buses and other drive vehicles, and truck body parts.

  In the present invention, the thermoplastic polymer mixture mainly contains an aromatic polycarbonate. The term polycarbonate includes homopolycarbonates and copolycarbonates. The polycarbonate may be linear or branched in a known manner. Polycarbonate has a molecular weight of 5,000 to 80,000, preferably 10,000 to 40,000 as determined by gel permeation chromatography. The molecular weight is particularly preferably 15,000 to 35,000, in particular 15,000 and 22,000.

  The polycarbonate is prepared in a known manner from diphenols, carbonic acid derivatives and optionally chain terminators and optionally branching agents.

  Details regarding the production of polycarbonate have been described in numerous patents for about 40 years. By way of example only, Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964 By Dr. D. Freitag, U. Grigo, PR Muller, N. Nouvertne, Bayer Aktiengesellschaft , `` Polycarbonates '', Encyclopedia of Polymer Science and Engineering, Volume 11, 2nd Edition, 1988, pages 648-718, and finally, Dress (Dres.) "Polycarbonate" by U. Grigo, K. Kirchner and P.R.Müller, Beck -/ Brown, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetal, Polyester, Celluloseester, Karl Hanser Ferlach, Munich, Vienna 1992 Year, see pages 117-299.

  Suitable diphenols for making polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis- (hydroxyphenyl) -alkane, bis- (hydroxyphenyl) -cycloalkane, bis- (hydroxyphenyl) -sulfide, bis -(Hydroxyphenyl) -ether, bis- (hydroxyphenyl) -ketone, bis- (hydroxyphenyl) -sulfone, bis- (hydroxyphenyl) -sulfoxide, and α, α'-bis- (hydroxyphenyl) -diisopropylbenzene As well as these nuclear alkylated and ring halogenated compounds.

  Particularly preferred phenols are 4,4′-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis. -(4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane Bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4- Hydroxyphenyl) -sulfone, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -p- Diisopropylbenzene, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, 1,1-bis -(4-Hydroxy Ciphenyl) -3,3,5-trimethylcyclohexane and 4,4 '-(m-phenylenediisopropylidene) -diphenol.

  Particularly preferred diphenols are 2,2-bis- (4-hydroxyphenyl) -propane (BPA), 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis -(3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, 4,4 '-(m-phenylenediisopropylidene) -Bisphenol (CAS-No.13595-25-0) (BPM), 1,1-bis- (4-hydroxyphenyl) -cyclohexane and 1,1-bis- (4-hydroxyphenyl) -3,3,5 -Trimethylcyclohexane (TMC).

  Examples of the diphenols and suitable diphenols include, for example, U.S. Patent Nos. 3028635 and 2999835, 3148172, 29011273, 3271367, and 4982014. No. 2999846, German Patent Application Publication No. A1570703, No. 2063050, No. 2036052, No. 2211956, No. 2211956 and No. 15532396, French Patent No. 1561518 Publication, paper "Schnell, Chemistry and Physics of Polycarbonates", InterScience Publishers, New York 1964 ", and JP 61 (1986) -62039 No. 61 (1986) -62040 and 61 (1986) -105550.

  In the case of homopolycarbonate, only one kind of diphenol is used, and in the case of copolycarbonate, a plurality of diphenols are used.

  Group consisting of at least one polycarbonate and a diol unit comprising BPA and / or trimethylcyclohexyl-bisphenol (TMC), preferably a homopolymer of BPA, a copolymer of BPA and TMC or a copolymer containing 5-60% TMC Polymer mixtures containing more selected are preferably used.

  Suitable carbonic acid derivatives include, for example, phosgene or diphenyl carbonate.

  Suitable chain terminators include monophenols and monocarboxylic acids. Suitable monophenols include phenol itself, cresol, p-tert-butylphenol, pn-octylphenol, p-iso-octylphenol, pn-nonylphenol and p-iso-nonylphenol, and p-cumylphenol. Halogen phenols such as alkylphenols, p-chlorophenol, 2,4-dichlorophenol, p-bromophenol amylphenol and 2,4,6-tribromophenol, and mixtures thereof.

ここで、Ｒは、水素、tert-ブチルまたは分枝もしくは非分枝のＣ_８および／またはＣ_９アルキル基を表す。しかし、ｐ-クミルフェノールも好ましく使用され得る。エステル交換反応の場合、連鎖停止剤は、使用されるジアリールカーボネートからもたらされる。 A preferred chain terminator is a phenol of formula (I).

Here, R represents hydrogen, tert-butyl or a branched or unbranched C ₈ and / or C ₉ alkyl group. However, p-cumylphenol can also be preferably used. In the case of transesterification, the chain terminator is derived from the diaryl carbonate used.

  The amount of the chain terminator used is preferably 0.1 mol% to 5 mol% with respect to 1 mol of diphenol used in the phase interface method. Chain terminators may be used before, during or after phosgenation.

  Suitable branching agents are trifunctional or higher functional compounds known from polycarbonate chemistry, in particular those having three or more phenolic OH groups.

  Suitable branching agents are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane-2, 4,6-dimethyl-2,4,6-tri- ( 4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -Phenylmethane, 2,2-bis- [4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol, 2,6- Bis- (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, hexa- (4- (4-hydroxy Phenyl-isopropyl) -phenyl-orthoterephthalate, tetra- (4-hydroxyphenyl) -methane, tetra- (4- (4-hydroxyphenyl-isopropyl) -phenoxy ) -Methane and 1,4-bis- (4 ', 4' '-dihydroxytriphenyl) -methyl) -benzene and 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid chloride, and some In this application, 3,3-bis- (3-methyl-4-hydroxy-phenyl) -2-oxo-2,3-dihydroindole is also preferably included.

  The amount of branching agent optionally used is 0.01 mol% to 2 mol% with respect to 1 mol of diphenol used.

  In the phase boundary method, the branching agent may be contained in the alkaline aqueous phase together with the diphenol and the chain terminator, or may be dissolved in addition to the organic solvent. In the case of transesterification, the branching agent may be used with diphenols.

  The person skilled in the art is familiar with all the above-mentioned methods for producing thermoplastic polycarbonates.

  The compound used as a release agent is preferably an ester of a polyhydric alcohol and a long chain carboxylic acid. A release agent that is not completely esterified and therefore has a free OH group is preferred. A (partial) ester of a saturated monovalent fatty acid having 16 to 22 carbon atoms and glycerol, trimethylolpropane, pentaerythritol or similar polyhydric alcohol is particularly preferred. In particular, glycerol monostearate and glycerol monopalmiate.

  The saturated monovalent fatty acid ester of glycerol is used alone or as a mixture containing two or more components. Saturated monoesters of glycerol are usually produced by transesterification of hydrogenated animal or vegetable oils with glycerol. This reaction product also contains an ester other than the glycerol ester, which is used as the release agent of the present invention. For example, the mixture may contain a lower or higher proportion of diglycerides and triglycerides.

  During the manufacture of CDs and other optical storage media (such as DVDs), the optimum amount of release agent is determined on the one hand by a suitable release action and on the other hand by the formation of a film on the mold. The conventionally used concentration of release agent is 50 to 1,000 ppm, more preferably 100 to 500 ppm. In other applications of polycarbonate, this concentration is from 100 to 10,000 ppm, preferably from 2,000 to 7,000 ppm.

前記式中、ｎは、０〜５までの数、好ましくは１〜３、特に好ましくは３を表し、Ｙはそれぞれ、互いに独立して、アルキルまたは任意に置換されたアリール、好ましくはＣ_１〜Ｃ_４アルキル、特に好ましくはメチル、sec-ブチルおよびtert-ブチルを表し、ｍは、１〜３の数、好ましくは３を表し、およびＸはそれぞれ互いに独立して、任意に置換されたメチレン基を表し、ここで、少なくとも１個のメチレン基は完全に置換されていなければならず、および前記置換基はそれぞれ、互いに独立して、Ｃ_１〜Ｃ_２０アルキルから成る群より選択され、好ましくは完全に置換されたメチレン基におけるＣ_１〜Ｃ_２０アルキルまたは２個の置換基は、基：

で表される。この基において、Ｒ^１は、Ｃ_１〜Ｃ_１８アルキル基、Ｃ_３〜Ｃ_１２シクロアルキル基、Ｃ_６〜Ｃ_３０脂肪芳香族基およびアリール（これらの基は１〜４個のＯ-アルキレン-Ｏおよび／またはカルボン酸エステル-ＣＯＯ-基で置換されていてよい。）、ＯＨ基を２〜１０個含有するＣ_２〜Ｃ_１８ポリヒドロキシアルキル基、フェノール性ＯＨ基を２〜１０個含有するＣ_２〜Ｃ_１８ポリフェニル基から成る群より選択される。 The special phosphite of the present invention has both an aromatic group and an aliphatic group in one molecule. This is represented by the following structural formula.

In the above formula, n represents a number from 0 to 5, preferably 1 to 3, particularly preferably 3, and each Y independently of one another is alkyl or optionally substituted aryl, preferably C _1- C ₄ alkyl, particularly preferably methyl, sec-butyl and tert-butyl, m represents a number from 1 to 3, preferably 3, and X each independently of one another is an optionally substituted methylene group Wherein at least one methylene group must be fully substituted, and each said substituent, independently of one another, is selected from the group consisting of C ₁ -C ₂₀ alkyl, preferably C ₁ -C ₂₀ alkyl or two substituents in the fully substituted methylene group, group:

It is represented by In this group, R ¹ is a C ₁ -C ₁₈ alkyl group, a C ₃ -C ₁₂ cycloalkyl group, a C ₆ -C ₃₀ aliphatic aromatic group and an aryl (these groups are represented by 1-4 O-alkylene- O and / or carboxylic acid ester-COO- groups may be substituted.), C ₂ -C ₁₈ polyhydroxyalkyl groups containing 2-10 OH groups, 2-10 phenolic OH groups It is selected from the group consisting of C ₂ -C ₁₈ polyphenyl group.

ここで、Ｒ_２は、Ｃ_１〜Ｃ_６アルキルを表し、Ｒ_３は、メチルまたはエチルを表し、およびＲ_４は、Ｃ_１〜Ｃ_１８アルキル基、Ｃ_３〜Ｃ_１２シクロアルキル基、Ｃ_６〜Ｃ_３０脂肪芳香族基およびアリール基（これらの基は１〜４個のＯ-アルキレン-Ｏおよび／またはカルボン酸エステル-ＣＯＯ-基で置換されていてよい。）、ＯＨ基を２〜１０個含有するＣ_２〜Ｃ_１８ポリヒドロキシアルキル基、フェノール性ＯＨ基を２〜１０個含有するＣ_２〜Ｃ_１８ポリフェニル基から成る群より選択される。 Preferred compounds are those of the formula

Here, R ₂ represents C ₁ -C ₆ alkyl, R ₃ represents methyl or ethyl, and R ₄ represents a C ₁ -C ₁₈ alkyl group, a C ₃ -C ₁₂ cycloalkyl group, C ₆ -C ₃₀ aliphatic aromatic group and an aryl group (these groups may be substituted with 1-4 O- alkylene -O and / or carboxylic acid ester -COO- group.), 2-10 an OH group pieces containing to _C 2 _{-C 18} polyhydroxyalkyl radical, selected from the group consisting of _C 2 _{-C 18} polyphenyl group containing 2 to 10 phenolic OH groups.

式中、Ｙおよびｎは前記と同じ意味を表し、およびＲ_５は、互いに独立して、水素およびＣ_３〜Ｃ_２０アルキルから成る群より選択され、少なくとも１個のＲ_５は好ましくはアルキルを表し、Ｒ_６は、互いに独立して、Ｃ_１〜Ｃ_１０アルキルを表す。 Also preferred are compounds of the following formula:

In which Y and n represent the same meaning as above, and R ₅ , independently of one another, is selected from the group consisting of hydrogen and C ₃ -C ₂₀ alkyl, and at least one R ₅ preferably represents alkyl. And R ₆ independently represents C ₁ -C ₁₀ alkyl.

式中、Ｒ_１およびＲ_２は、メチル、serc-ブチルまたはtert-ブチルを表す。 Particularly preferred are compounds of the formula

In the formula, R ₁ and R ₂ represent methyl, serc-butyl or tert-butyl.

  Similarly, the compounds described in Examples on pages 16 to 20 and 21 of EP-A-10038876 are particularly preferred.

Most preferred is (2,4,6-tri-t-butylphenyl)-(2-butyl-2-ethyl-propane-1,3-diyl) -phosphite represented by the following structural formula.

  The phosphite may be used alone, but may be used in combination with other phosphorus compounds. Here, the other phosphorus compounds may have different phosphorylation numbers. Therefore, combinations of the phosphites of the present invention with other phosphites, phosphines such as triphenylphosphine, phosphonites, phosphates, phosphonates, etc. may also be used.

  The phosphites used in the present invention may be produced in a generally known or similarly known manner. (2,4,6-Tri-t-butylphenyl)-(2-butyl-2-ethyl-propane-1,3-diyl) -phosphite is described, for example, in European Patent Application Publication No. A702018 and European Patent This is described in Japanese Patent No. 635514.

  The polymer mixtures according to the invention generally contain phosphorus compounds in a proportion of 10 to 5,000 ppm, preferably 10 to 1,000 ppm, particularly preferably 20 to 500 ppm, most preferably 50 to 250 ppm.

  The compounds having preferred, particularly preferred or most preferred substances described hereinafter are preferred, particularly preferred or most preferred.

  However, the definitions and explanations of the groups and the parameters or quantitative ratios in the above-mentioned generally described or preferred ranges may be combined with each other as desired, in other words between each range and the preferred range. .

  The release reagent and the phosphorus compound are added to the thermoplastic polymer mixture. Preferably, they are added after the production of the polycarbonate and during purification, such as by addition to the melt of a polycarbonate polymer solution or thermoplastic polymer mixture. Furthermore, the components can be added independently of one another at various stages of operation. For example, if all the components are included in the production of the final product (molded product), one of the components is added during the purification of the polymer solution and the other component is added to the melt.

  The thermoplastic polymer mixture of the present invention may contain known amounts of general-purpose additives for polycarbonate, preferably UV stabilizers, flame retardants, dyes, fillers, foaming agents, fluorescent whitening agents and charging agents. Examples include inhibitors. In optical applications, it is preferable to use components that do not adversely affect the transparency of the material.

  These substances are described in many publications such as John Murphy, Additives for Plastics Handbook 1999, and are commercially available.

1. Suitable antioxidants include, for example:
1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methyl- (Cyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenol, Those whose side chains are linear or branched (eg 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) -Phenol, 2,4-dimethyl-6- (1'-methylheptadecy-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) -fur Nord).

1.2. Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6- Didodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6- Diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3 , 5-Di-tert-butyl-4-hydroxyphenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols , for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers such as 2,2'-thio-bis- (6-tert-butyl-4-methylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio -Bis- (6-tert-butyl-3-methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thio-bis- (3, 6-di-sec-amylphenol), 4,4′-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidene bisphenols such as 2,2'-methylene-bis- (6-tert-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2,2 '-Methylene-bis- [4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene- Bis- (6-nonyl-4-methylphenol), 2,2'-methylene-bis- (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis- (4,6-di-) tert-butylphenol), 2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis- [6- (α-methylbenzyl) -4-nonylphenol] 2,2′-methylene-bis- [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4′-methylene-bis- (2,6-di-tert-butylphenol), 4'-methylene-bis- (6-tert-butyl-2-methylphenol), 1,1-bis- (5-tert-butyl-4- Droxy-2-methylphenyl) butane, 2,6-bis- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris- (5-tert- Butyl-4-hydroxy-2-methylphenyl) -butane, 1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis- [ 3,3-bis- (3′-tert-butyl-4′-hydroxyphenyl) -butyrate], bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) -dicyclopentadiene, bis- [ 2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2- Hydroxyphenyl) -butane, 2,2-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) -propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-) Methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-teto - (5-tert-butyl-4-hydroxy-2-methylphenyl) - pentane.

1.7. O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethyl Benzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis- (4-tert- Butyl-3-hydroxy-2,6-dimethylbenzyl) -dithioterephthalate, bis- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4 -Hydroxybenzyl mercaptoacetate.

1.8. Hydrobenzylated malonate such as dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl -4-hydroxy-5-methylbenzyl) malonate, didodecyl mercaptoethyl-2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis- [4- (1,1 , 3,3-tetramethylbutyl) phenyl] -2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds such as 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis- (3 , 5-Di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) ) -Phenol.

1.10. Triazine compounds such as 2,4, -bis- (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto- 4,6-bis- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis- (3,5-di- tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- (4-tert-butyl-3-hydroxy-2,6 -Dimethylbenzyl) isocyanurate, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris- ( 3,5-di-tert-butyl-4-hydroxyphenylpropioyl) -hexahydro-1,3,5-triazine, 1,3,5-tris- (3,5-dicyclohexyl-4-hydride Kishibenjiru) - isocyanurate.

1.11. Acylaminophenols , such as 4-hydroxylauranilide, 4-hydroxytearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamate .

1.12. β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ester , monohydric or polyhydric alcohol (eg methanol, ethanol, n-octanol, i-octanol, octadecanol) 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N′-bis- (hydroxyethyl) -oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7 -Esters with trioxabicyclo [2.2.2] octane). The ester of octadecanol (Ciba Spec (Ciba Spec.) Ltd. IRGANOX1076 ^{(registered trademark))} is and preferred particularly preferred.

1.13. β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid ester , monohydric or polyhydric alcohol (eg methanol, ethanol, n-octanol, i-octanol, octadecanol) 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N′-bis- (hydroxyethyl) -oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7 -Esters with trioxabicyclo [2.2.2] octane).

1.14. β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid, a mono- or polyhydric alcohol (eg methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) ) -Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane ) And ester.

1.15. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid , which are mono- or polyhydric alcohols (eg methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9 -Nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) -Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxa-bicyclo [2.2.2] octane) And ester.

1.16. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid , for example N, N′-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl)- Hexamethylene diamide, N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylene diamide, N, N'-bis- (3,5-di-tert-butyl -4-hydroxyphenylpropionyl) hydrazide, N, N′-bis- [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) -ethyl] oxamide (Uniroyal ) Naugard ^{(registered trademark)} XL-1).

1.17. Ascorbic acid (vitamin C)

1.18. Amino acid inhibitors , for example, N, N′-diisopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N, N′-bis- (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis- (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis- (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis- (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p -Phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methyl-heptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N '-Phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) -diphenylamine, N, N '-Dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) ) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine (eg, p, p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoyl) -Aminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis- (4-methoxyphenyl) -amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4 '-Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis-[(2-methylphenyl Nyl) -amino] -ethane, 1,2-bis- (phenylamino) -propane, (o-toluyl) -biguanide, bis- [4- (1 ′, 3′-dimethylbutyl) -phenyl] -amine, tert-octylated N-phenyl-1-naphthylamine), mono- and di-alkylated tert-butyl / tert-octyl diphenylamine mixtures, mono- and di-alkylated nonyl diphenylamine mixtures, mono- and di-alkylated A mixture of dodecyldiphenylamine, a mixture of mono- and di-alkylated isopropyl / isohexyldiphenylamine, a mixture of mono- and di-alkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1 , 4-Benzothiazine, phenothiazine, mono- and di-alkylated tert-butyl / tert-octylphenothiazine, tert-octylphenothiazine, mono- and di-alkyl A mixture of tert-octylphenothiazine, N-allylphenothiazine, N, N, N ′, N′-tetraphenyl-1,4-diaminobut-2-ten, N, N′-bis- (2,2,6,6 -Tetramethylpiperidi-4-yl) -hexamethylenediamine, bis- (2,2,6,6-tetramethylpiperidi-4-yl) sebacate, 2,2,6,6-tetramethylpiperidi 4-None, 2,2,6,6-tetramethylpiperidin-4-anol. These compounds may be used alone or as a mixture.

1.19. Suitable thiosynergists are, for example, dilauryl thiodipropionate and / or distearyl thiodipropionate.

2. UV-absorbers and light stabilizers may be used in the composition of the present invention in an amount of 0.1 to 15% by weight, preferably 3 to 8% by weight, based on the weight of the composition. Suitable UV absorbers and light stabilizers are, for example:

2.1. 2- (2'-hydroxyphenyl) -benzotriazole , such as 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3 ', 5'-di-tert-butyl-2' -Hydroxyphenyl) -benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-5 '-(1,1,3,3-tetramethyl) (Butyl) -phenyl) -benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'- Hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy- 4'-octyloxyphenyl) -benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) -benzotriazole, 2- (3', 5'-bis- (α, α-Dimethylbenzyl) -2'-hydroxypheny ) -Benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) -phenyl-5-chlorobenzotriazole, 2- (3'-tert-butyl- 5 '-[2- (2-Ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-( 2-methoxycarbonylethyl) -phenyl) -5-chlorobenzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) -phenyl) -benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) -phenyl) -benzotriazole, 2- (3'-tert-butyl-5'-[2- (2- Ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (3'-tert -Butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) -phenylbenzotriazole, 2,2'-methylene-bis- [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol], and 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole and polyethylene glycol 300 Of the transesterification reaction product, and [R—CH ₂ CH ₂ —COO—CH ₂ CH ₂ ] ₂ , wherein R is 3′-tert-butyl-4′-hydroxy-5 ′ -2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3 '-(α, α-dimethylbenzyl) -5'-(1,1,3,3-tetramethylbutyl) -Phenyl] -benzotriazole), 2- [2'-hydroxy-3 '-(1,1,3,3-tetramethylbutyl) -5'-(α, α-dimethylbenzyl) -phenyl] -benzotriazole ).

2.2. 2-hydroxybenzophenone , such as 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- And 2'-hydroxy-4,4'-dimethoxy-derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids , such as 4-tert-butylphenyl salicylic acid ester, phenyl salicylic acid ester, octylphenyl salicylic acid ester, bibenzoyl resorcinol, bis- (4-tert-butylbenzoyl) -resorcinol, benzoyl Resorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl 4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl 4-hydroxybenzoate, octadecyl-3 , 5-Di-tert-butyl 4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3.5-di-tert-butyl 4-hydroxybenzoate.

2.4. Acrylic esters such as ethyl-α-cyan-β, β-diphenyl acrylate, isooctyl-α-cyan-β, β-diphenyl acrylate, methyl-α-carbomethoxycinnamate, methyl-α-cyan-β- Methyl-p-methoxycinnamate, butyl-α-cyan-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β- Cyanvinyl) -2-methylindoline.

2.5. A nickel complex, for example a nickel complex such as a 1: 1 or 1: 2 complex with 2,2′-thiobis- [4- (1,1,3,3-tetramethylbutyl) -phenol], wherein n -With or without another ligand such as butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salt of monoalkyl ester, for example 4-hydroxy-3,5-di- a methyl or ethyl ester of tert-butylbenzylphosphonic acid, a nickel complex of ketoxime such as 2-hydroxy-4-methylphenylundecylketoxime, a nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, With or without another ligand.

2.6. Sterically hindered amines such as bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacic acid ester, bis- (2,2,6,6-tetramethyl-4-piperidyl) succinic acid ester, Bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacic acid ester, bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacic acid ester, bis -(1,2,2,6,6-pentamethyl-4-piperidyl), n-butyl-3,5-di-tert-butyl-4-hydroxy-benzylmalonate, 1- (2-hydroxyethyl) Condensate of -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene Linear or cyclic condensate of diamine with 4-tert-octylamino-2,6-di-chloro-1,3,5-triazine, tris- (2,2,6,6-tetramethyl-4- Piperidyl) -nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl (Lu-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '-(1,2-ethanediyl) -bis- (3,3,5,5-tetramethylpiperazinone) 4-benzoyl- (2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis- (1,2,2,6,6-pentamethyl Piperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonic ester, 3-n-octyl-7,7,9,9-tetramethyl-1, 3,8-triazaspiro [4.5] decane-2,4-dione, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacic acid ester, bis- (1-octyloxy-2, 2,6,6-tetramethylpiperidyl) succinate, N, N′-bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-morpholino-2,6- Linear or cyclic condensate with dichloro-1,3,5-triazine, 2-chloro-4,6-bis- (4-n-butylamino -2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) -ethane condensate, 2-chloro-4,6- Between bis- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) -ethane Condensate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] -decane-2,4-dione, 3-dodecyl-1- (2, 2,6,6-tetramethyl-4-piperidyl) -pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) -pyrrolidine-2, A mixture of 5-dione, 4-hexadecyloxy-2,2,6,6-tetramethylpiperidine and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N′-bis- ( 2,2,6,6-tetramethyl-4-piperidyl) -condensation product of hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2 Of 2-bis- (3-aminopropylamino) -ethane with 2,4,6-trichloro-1,3,5-triazine and further 4-butylamino-2,2,6,6-tetramethylpiperidine Product (CAS standard No. [136504-96-6]), N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecyl-succinimide, N- (1,2,2,6) , 6-pentamethyl-4-piperidyl) -n-dodecyl-succinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4.5] decane, 7 , 7,9,9-Tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4.5] decane and epichlorohydrin, 1,1-bis- (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) -ethane, N, N′-bis- (formyl) -N, N′-bis- ( 2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine, 4-methoxymethylenemalonic acid and 1,2,2,6,6- Diester with pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl) -siloxane], maleic anhydride-α-olefin copolymer and Reaction product with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides such as 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′- Didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) -oxamide, 2-ethoxy-5-tert -Butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxydisubstituted oxanilide and o- and p- Mixture of ethoxy disubstituted oxanilides.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazine , for example 2,4,6-tris- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4-octyloxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis -(2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis- (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3 , 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) 4,6-bis- (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxy) Phenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis- (2, 4-Dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butoxypropoxy) -phenyl] -4,6-bis- (2,4-dimethyl) Til) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) -phenyl] -4,6-bis- (2,4-dimethyl)- 1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) -phenyl] -4,6-bis- (2,4-dimethylphenyl) -1,3,5 -Triazine, 2- (2-hydroxy-4-hexyloxy) -phenyl-4,6-diphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6- Diphenyl) -1,3,5-triazine, 2,4,6-tris- [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) -phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethyl) Hexyl-1-oxy) -2-hydroxypropyl oxy] - phenyl} -4,6-bis - (2,4-dimethylphenyl) -1,3,5-triazine.
These compounds may be used alone or as a mixture.

3. Suitable metal deactivators include , for example, N, N′-diphenyloxyamide, N-salicylal-N′-salicyloyl hydrazine, N, N′-bis- (Salicyl oil) hydrazine, N, N′-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicil oil amino-1,2,4-triazole, bis- (benzylidene) ) -Oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-diacetyladipoyl dihydrazide, N, N'-bis- (salicyloyl) -oxalyl dihydrazide, N, N'-bis- (Salicyl oil) -thiopropionyl dihydrazide. These compounds may be used alone or as a mixture.

4). Suitable peroxide collectors include, for example, esters of β-thiodipropionic acid, such as lauryl-, stearyl-, myristyl- or tridecyl-esters, mercaptobenzimidazoles, or zinc salts of 2-mercaptobenzimidazoles. , Zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (dodecyl mercapto) propionate. These compounds may be used alone or as a mixture.

5. Suitable basic co-stabilizers include, for example, melamine, polyvinyl pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, higher fatty acid alkali and alkaline earth metal salts ( For example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate), antimony pyrocatecholate or zinc pyrocatecholate. These compounds may be used alone or as a mixture.

6). Suitable nucleating agents include inorganic substances such as talc, metal oxides (eg titanium dioxide or magnesium oxide), phosphates, carbonates or sulfates, preferably these alkaline earth metal salts, -Organic compounds such as poly-carboxylic acids and their salts (eg 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate) and polymers such as ionic copolymers (ionomers) A compound. 1,3: 2,4-bis- (3 ', 4'-dimethylbenzylidene) -sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) -sorbitol and 1,3: 2,4-di (Benzylidene) -sorbitol is particularly preferred. These compounds may be used alone or as a mixture.

7). Suitable fillers and reinforcing agents are, for example, calcium carbonate, silicates, glass fibers, glass balloon flakes, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon Black, graphite, wollastonite, and sawdust and other natural product fibers, synthetic fibers. These compounds may be used alone or as a mixture.

8). Other suitable additives are , for example, plasticizers, lubricants, emulsifiers, pigments, viscosity modifiers, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and swelling agents.

などのラクトン系酸化防止剤である。前記化合物は、例えば、酸化防止剤として作用する。これらの化合物は単独でまたは混合物として使用されてよい。 10. Suitable benzofuranones and indolinones include, for example, U.S. Pat.Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643, German Patent Invention No. A4316611, A4316622, A4316876, European Patent Application Publication No. A0589839 or A0591102, or 3- [4- (2-acetoxyethoxy) -phenyl] -5, 7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) -phenyl] -benzofuran-2-one, 3,3 ′ -Bis- [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] -phenyl) -benzofuran-2-one], 5,7-di-tert-butyl-3- [4 -Ethoxyphenyl) -benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl -4-Pivaloyloxy Enyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (2 , 3-Dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one,

Lactone antioxidants such as The compound acts as an antioxidant, for example. These compounds may be used alone or as a mixture.

10. Suitable fluorescent plasticizers are listed in the "Plastics Additives Handbook", edited by Earl Gechter and H. Müller, Hanser Ferlark, 3rd edition, 1990, pages 775-789. Is.

11. Suitable flame retardants include phosphoric acid esters, i.e., triphenyl phosphate, resorcinol diphosphate, brominated phosphoric acid esters, bromine-containing compounds such as brominated oligocarbonate and the polycarbonate, and ^{_{C 4 F 9 SO 3 - Na}} + Such as salt.

12 Suitable brittle toughening agents include butadiene rubber containing grafted styrene-acrylonitrile or methyl methacrylate, ethylene / propylene rubber containing grafted maleic anhydride, ethyl- and butyl-acrylate rubber containing grafted methyl methacrylate or styrene-acrylonitrile, Includes permeable siloxanes and acrylate networks containing grafted methyl methacrylate or styrene-acrylonitrile.

13. Suitable polymers are produced by SAN, ABS, PMMA, PTFE, PSU, PPS, polyolefins such as polyethylene, polypropylene and ethylene / propylene rubber, epoxy resins, polyesters such as PBT, PET, PCT, PCTG and PETG, and interfacial methods Other polycarbonates.

14 Suitable antistatic agents are sulfonates, for example the tetraethylammonium salt of C ₁₂ H ₂₅ SO ^3- or C ₈ F ₁₇ SO ^3- .

15. Suitable colorants include pigments and organic and inorganic dyes.

16. Compounds containing epoxy groups , such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, copolymers of glycidyl methacrylate and epoxysilane.

17. Compounds containing anhydride groups such as maleic anhydride, succinic anhydride, benzoic anhydride and phthalic anhydride.

18. Phosphites and phosphonites suitable as stabilizers are, for example, triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite. Phyto, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) Pentaerythritol diphosphite, bis (2,4,6-to) Lis (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbite triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, 6-isooctyloxy-2 , 4,8,10-Tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl -12-methyl-dibenz [d, g] -1,3,2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis- (2,4 -Di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenz [d, g] -1,3,2-di Oxaphosphocin, 2,2 ', 2' '-nitrilo [triethyltris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite ], 2-ethyl-hexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-di Yl) phosphite, including 5-butyl-5-ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxaphosphirane. Or it may be used as a mixture.

Tris - (2,4-di -tert- butylphenyl) phosphite (Ciba - Geigy Irgafos ^(R) 168) or triphenylphosphine are particularly preferred.

  The 16 and 17 group compounds act as melt stabilizers. These compounds may be used alone or as a mixture.

  Of the above additives, those skilled in the art will obviously select suitable additives that do not reduce transparency in applications in the field of CD, DVD and other optical recording media.

It said IRGANOX1076 ^{(registered trademark)} and benzotriazole from the 2.1 group (so-called Tinuvin), especially mixtures thereof each other is the most preferred additive.

  The polymer mixtures according to the invention are used in a known manner in molded articles, preferably polycarbonates for producing optical media. In particular, it is used when manufacturing not only compact discs and DVDs but also optical media that can be written and erased once or more. The writing layer consists in particular of a dye or metal layer. The latter uses a change from an amorphous state to a crystalline state as a recording principle or has a magnetic property.

  The production of the optical medium preferably results from the polymer mixture of the invention previously produced as granules. However, optical media can also be produced by incorporating the components into pure or commercially available polycarbonates and / or additives commonly used in the production of molded articles from polycarbonate.

  The invention therefore also relates to shaped articles such as optical data carriers obtained from the thermoplastic polymer mixtures according to the invention, preferably compact discs and DVDs.

  The thermoplastic polymer mixture of the present invention has the advantages that it has thermal stability during the production of a molded product, and that the resulting final product (molded product) can be easily peeled off from the production mold and does not leave any damage to the mold. Have.

  The following examples illustrate the invention. However, the present invention is not limited to these examples.

Example:
Example of polycarbonate produced by the phase boundary method The following mixture is produced:
Polycarbonate with an average solution viscosity of 1.195 (measured at 25 ° C. at a concentration of 0.5 g in 100 mL of methylene chloride) prepared by phase boundary method from BPA-PC having tert-butylphenol end groups according to the following table The granule content (weight) x was thoroughly mixed with the glycerol monostearate content (weight) y and the phosphorus compound content (weight) z in a closed container. This mixture was then compounded in a Werner Pfleiderer ZSK53 twin screw kneader at a mass temperature of about 240 ° C.

  The product Loxiol EP129 from Henkel KgaA was used as glycerol monostearate. Phosphite 1 is (2,4,6-tri-tert-butyl-phenyl)-(2-butyl-2-ethyl-propane-1,3-diyl) -phosphite, which is Ultranox641 ( (Registered trademark) available from GE Specialty Chemicals. Phosphite 2 is tris (2,4-di-tert-butylphenyl) phosphite, which is available from Ciba-Geigy as Irgafos168®.

In order to measure the product stability of the CD, a CD blank made of the above material was produced on a Nestal Discjet 600 type CD injection molding machine. This CD had a thickness of 1.2 mm and an outer diameter of 120 mm. Product stability was tested under various machine conditions from settings 1 to 4 shown below.
Setting 1:
Cylinder temperature (supply / compression / cylinder head / nozzle) 315/320/320/320 ° C., maximum injection speed 130 mm / s, mold (preliminary working temperature) 55 ° C., cycle time 4.6 seconds
Setting 2:
Cylinder temperature (supply / compression / cylinder head / nozzle) 315/340/350/350 ° C., maximum injection speed 110 mm / second, mold (preliminary working temperature) 55 ° C., cycle time 4.9 seconds
Setting 3:
Cylinder temperature (supply / compression / cylinder head / nozzle) 315/360/380/380 ° C., maximum injection speed 100 mm / second, mold (preliminary working temperature) 55 ° C., cycle time 5.5 seconds
Setting 4:
Same as setting 2 except the cycle was interrupted by a 5 minute machine stop. After restarting the injection molding machine, a fifth supply was made for the following measurements.

Thereafter, the residual glycerol monostearate content and phenolic OH group content in the CD blank were determined. The following results were obtained.

The concentration of phenolic OH groups in CD was also measured under various conditions after production.

被膜形成は、以下の通り求めた。鋳型内での被膜を決定するために、１０００枚の部分充填ＣＤブランクを、AxxiconＣＤ鋳型を含むNestal Discjet600型ＣＤ射出成形機で製造した。ＣＤの約８０％部分充填は、計量供給パスを減量しかつフォローアップ圧を適合することにより達成した。シリンダー温度は、供給領域では３００℃および圧縮領域では３１０℃であり、シリンダーヘッドとノズルでは３３０℃の温度とした。サイクル時間は約５．５秒であった。１０００回目のショット後、ダイと外側領域（すなわち、ポリカーボネート溶融物と接触していない領域）のレベルの表面を被膜形成について目視観察した。前記結果が得られた。

The film formation was determined as follows. To determine the coating in the mold, 1000 partially filled CD blanks were produced on a Nestal Discjet 600 type CD injection molding machine containing an Axxicon CD mold. About 80% partial filling of the CD was achieved by reducing the metering path and adapting the follow-up pressure. The cylinder temperature was 300 ° C. in the supply region and 310 ° C. in the compression region, and 330 ° C. in the cylinder head and nozzle. The cycle time was about 5.5 seconds. After the 1000th shot, the surface at the level of the die and the outer area (ie, the area not in contact with the polycarbonate melt) was visually observed for film formation. The results were obtained.

Example of polycarbonate produced by melt transesterification According to the following table, an average solution viscosity of 1.200 (by 0.5 g concentration in 100 ml of methylene chloride) produced by melt transesterification from BPA-PC with phenol end groups (Measured at 25 ° C.) of polycarbonate granules (weight) x was thoroughly mixed in a closed container with glycerol monostearate content (weight) y and phosphorus compound content (weight) z. This mixture was then compounded in a Warner-Fiderer ZSK53 twin screw kneader at a mass temperature of about 240 ° C.

  The product Loxiol EP129 from Henkel Commandand Gezelshaft Auf Aktien was used as glycerol monostearate. Phosphite 1 is (2,4,6-tri-tert-butyl-phenyl)-(2-butyl-2-ethyl-propane-1,3-diyl) -phosphite, which is Ultranox641 ( (Registered trademark) available from GE Specialty Chemicals. Phosphite 2 is tris (2,4-di-tert-butylphenyl) phosphite, which is available from Ciba-Geigy as Irgafos168®.

  In order to measure the product stability of the CD, a CD blank made of the above material was produced on a Nestal Discjet 600 type CD injection molding machine. This CD had a thickness of 1.2 mm and an outer diameter of 120 mm. Product stability was evaluated in machine setting 3 of the machining program.

Thereafter, the residual glycerol monostearate content in the CD blank was determined. The following results were obtained.

Determination of the amount of condensate:
The amount of condensate was determined by weighing the aluminum foil with and without the coating. The amount of coating is defined as follows.

Detailed description of the process:
After drying (120 ° C., 4 hours), 20 g of granulated material was poured into an aluminum pan having a diameter of 80 mm and a depth of 15 mm so that the bottom of the pan was evenly coated with the granulated material. The filled dish was placed in a custom sample chamber (85 mm diameter, 50 mm depth) of an electrically heated metal block and closed with aluminum foil having a thickness of 0.03 mm and a diameter of 100 mm. During the measurement, the foil was cooled with a cooling plate in order to concentrate the volatile components on the foil. The temperature of the cooling water was adjusted to 20 ° C. When performing the measurement, the aluminum foil must sufficiently block the sample chamber from the outside.
Heat the metal block to a temperature of 300 ° C. for several minutes. The sample was held at this temperature for 4 hours. The test apparatus was then cooled to ambient temperature. After reaching ambient temperature, the aluminum foil was removed and weighed with a microbalance, and the amount of condensate was calculated according to the above formula.

Detailed description of the measurement method:
Glycerol monostearate The glycerol monostearate was separated with a capillary by gas chromatography and detected with a flame ionization detector. This was evaluated by the internal standard method. The measurement limit was about 10 ppm.

Phenolic OH
The polycarbonate was dissolved in dichloromethane and reacted with titanium (IV) chloride to form an orange-red complex. The absorbance of this complex at 546 nm was measured with a photometer. Calibration was performed with BPA as an external standard. The measurement limit was about 20 ppm OH.

Claims (6)

At least one polycarbonate;
And monovalent fatty acids, saturated 16-22 C atoms, glycerol, partial esters of trimethylolpropane or pentaerythritol Le, at least one release agent and at least one represented by the following structural formula A thermoplastic polymer mixture containing a phosphite.

(Where
R ₅ , independently of one another, is selected from the group consisting of hydrogen and C ₃ -C ₂₀ alkyl;
R ₆ independently of one another represents C ₁ -C ₁₀ alkyl;
n is 0-5,
Y independently represents alkyl or aryl. )   The thermoplastic polymer mixture according to claim 1, wherein the release agent is glycerol monostearate or glycerol monopalmiate.   The thermoplastic polymer mixture according to claim 1 or 2, wherein the molecular weight of the polycarbonate is 15,000 to 35,000.   The thermoplastic polymer mixture according to any one of claims 1 to 3, comprising 0.01 to 1.5% by weight of a release agent and 0.001 to 0.1% by weight of a phosphite.   The manufacturing method of a molded article using the thermoplastic polymer mixture in any one of Claims 1-4.   5. An optical data carrier produced from the thermoplastic polymer mixture according to any of claims 1-4.